JPH087420B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to a developing method using a high silver chloride silver halide photographic light-sensitive material. The present invention relates to a development processing method having excellent desilvering property.

At the same time, it relates to an improved processing method for white background despite the rapid processing.

(Prior Art) In recent years, in the photographic processing of a color photographic light-sensitive material, it has been desired that the processing time be shortened as the delivery time for finishing and the labor for laboratories are reduced. As a method for shortening the time of each treatment step, a temperature increase and a replenishment amount increase are general methods, but in addition, many methods of strengthening stirring or adding various accelerators have been proposed.

Among them, for the purpose of accelerating color development and / or reducing the replenishment amount, a color photographic light-sensitive material containing a silver chloride emulsion in place of the silver bromide emulsion or silver iodide emulsion which has been widely used in the past is processed. It is known how to do it. For example, International Publication WO87-04534 describes a method of rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer containing substantially no sulfite ion and benzyl alcohol.

However, when rapid processing is performed by the above method,
In particular, during continuous processing, stains (coloring of the white background) are generated in the non-coloring areas (hereinafter referred to as white background) of the color photographic light-sensitive material, and the white background is contaminated. Further, desilvering failure occurs in the image area (coloring area). Occurs, and the color reproducibility and saturation decrease.
It turned out to be a significant problem.

The main cause of the above-mentioned stains is stains caused by so-called fog, which is caused by developing the unexposed portion with silver.

Color contamination due to the adherence of oxides (tar components, etc.) such as color developing agents to photosensitive materials.

After the color development process, the developing agent is brought into an oxidizing bath (bleaching solution or standard fixing solution), and the developing agent is oxidized, indiscriminately coupling with a coupler to form a dye, so-called bleach fog.

So-called residual color that remains even after processing due to insufficient cleaning of the anti-irradiation dye and sensitizing dye.

Etc., but in order to prevent pollution of white background, comprehensively improve and prevent the pollution caused by
It will be achieved for the first time.

On the other hand, the desilvering failure due to the high silver chloride emulsion is presumed to occur due to the following reasons.

That is, a silver chloride emulsion has a higher solubility of silver ions than silver iodobromide or silver chlorobromide emulsion, and as a result, dissolution physical development is remarkably promoted, and development is completed in a short time. The developed silver is unlikely to form a filament, and large developed silver having a small surface area and a spherical shape is produced. As a result, the desilvering rate is considered to be delayed.

As a method for solving the above problems, in a rapid processing method using a high silver chloride color photographic light-sensitive material, as a method for reducing fluctuations in photographic characteristics (particularly, fog) due to continuous processing, JP-A-58-58 It is known to use organic antifoggants in JP-A-95345 and JP-A-59-232342. However, it has been found that the use of an organic antifoggant tends to cause a decrease in the maximum density and also tends to cause desilvering failure.
It is by no means the preferred method.

Further, in JP-A-61-70552, a high silver chloride color photographic light-sensitive material is used, and a replenishing amount is added so that overflow does not occur in the developing bath during development. JP-A-63-106655 discloses a method of stabilizing a silver halide color photographic light-sensitive material having a high silver chloride content in a silver halide emulsion layer with a hydroxyamine compound for the purpose of stabilizing the processing. A method of developing with a color developer containing a chloride having a concentration of 2 × 10 ^-2 mol / l or more is disclosed.

However, none of the methods is satisfactory in preventing stain generation, and is not a satisfactory technique because it does not improve the desilvering property.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a development processing method using a high silver chloride color photographic light-sensitive material, which is rapid and prevents generation of stains. is there.

A second object of the present invention is to use a high silver chloride color photographic light-sensitive material and have excellent photographic properties with a high maximum density and a low minimum density in rapid processing, and fluctuations in photographic characteristics associated with continuous processing. It is an object of the present invention to provide a development processing method in which (especially minimum density) is significantly suppressed.

A third object of the present invention is to provide a development processing method which uses a high silver chloride color photographic light-sensitive material and has a small amount of residual silver and improved desilvering property.

(Means for Solving Problems) The above object is to treat a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent in an amount of 80 mol% or more. A silver halide color light-sensitive material having a high silver chloride silver halide emulsion composed of silver chloride in at least one layer and at least one compound represented by the following general formula (I) was used. ^{-2 to} 1.5 to 10 ^-1 mol / l content,
Further, it is effectively achieved by a processing method of a silver halide color photographic light-sensitive material characterized by processing with a color developing solution containing bromide ions in an amount of 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l. I found a thing.

General formula (I) Chloride ion is well known as one of the antifoggants, but its effect is small, and even if it is used in a large amount, the increase of fog due to continuous processing and the streak-like pattern that occurs when processed by an automatic processor Fogging was not completely prevented, but the development was delayed and the maximum density was lowered.

Bromine ions are also well known as one of the antifoggants, but depending on the addition amount, it is possible to prevent the fog due to continuous processing, that is, the fog due to development, but it suppresses development and suppresses the maximum density. In addition, the sensitivity was lowered and it was not practical.

On the other hand, in a silver halide color photographic light-sensitive material, sensitivity is lowered or latent image storability is deteriorated for the purpose of preventing irradiation at the time of exposure or printing and improving safety against so-called safe light. Or other adverse effects on photographic characteristics, and does not deteriorate the quality as stains (residual color) after processing.
Various dyes are used.

In the rapid processing, these dyes are insufficiently washed, or are eluted in the washing water of the color developing solution and / or in the stabilizing processing solution, and the processing solution is colored, or the processing agent color photographic light-sensitive material is colored. This may cause undesired stain, which is an important problem especially in rapid processing. For the purpose of preventing stains (color contamination) attributed to such dyes, it is generally preferable to use a dye that becomes colorless by decomposing with an alkali or a reducing agent in a color developing solution, but in rapid processing Especially, washing and bleaching of dyes in a color developing solution are important techniques.

In the present invention, by using a specific amount of chlorine ions and bromine ions in the color developing solution, without reducing the maximum concentration, succeeded in suppressing organic fog, and even in spite of rapid processing, It is possible to promote the cleaning effect of the above-mentioned dye of the general formula (I) in the color developing solution and at the same time to stop the release of the sensitizing dye, and as a result, to suppress the stain and to obtain, for example, an excellent white background. did it.

At the same time, it is worth noting that the chloride ion concentration, the bromine ion concentration of the present invention and the use of the dye of the above-mentioned general formula (I) significantly improved the desilvering property. In particular, it is noteworthy that such an effect could be achieved by the structure of the dye used in this way.

 The present invention will be described in detail below.

The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better.

The coated silver amount of the silver halide light-sensitive material of the present invention is 0.80 g / m ²
The following is preferable from the viewpoint of quickness, desilvering property and stain prevention. This is considered to be due to the effect of reducing the film thickness in addition to simply reducing the amount of silver. Coating silver amount 0.75 g / cm ²
The following is more preferable. Particularly preferably 0.65 g /
cm ² or less, and preferably 0.30 g / cm ² or more from the viewpoint of image density and the like.

In the present invention, chlorine ion is added to the color developer at 3.5.
It is necessary to contain x10 ^{-2 to} 1.5 to 10 ^-1 mol / l.
It is preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / l. When the chlorine ion concentration is more than 1.5 × 10 ⁻¹ mol / l, there is a drawback that the development is delayed, and the object of the present invention of rapid and high maximum concentration cannot be achieved. Further, if it is less than 3.5 × 10 ^-2 mol / l, stain cannot be prevented, and further, photographic property variation (especially minimum density) accompanying continuous processing is large, and the amount of residual silver is large. Does not achieve the purpose of.

In the present invention, a bromine ion of 3.0 is contained in the color developer.
It is necessary to contain x10 ^-5 mol / l to 1,0 x 10 ^-3 mol / l. It is preferably 5.0 × 10 ⁻⁵ × 5 × 10 ⁻⁴ mol / l. When the bromine ion concentration is more than 1 × 10 ^-3 mol / l, the development is delayed, the maximum concentration and sensitivity are lowered, and when it is less than 3.0 × 10 ^-5 mol / l, stain cannot be prevented and further Changes in photographic properties due to continuous processing (especially minimum density)
Also, desilvering failure cannot be prevented and the object of the present invention is not achieved.

Here, chlorine ions and bromine ions may be added directly to the developing solution or may be eluted from the light-sensitive material during the development processing.

When added directly to the color developing solution, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Among them, preferred is sodium chloride. , Potassium chloride.

Also, it may be supplied in the form of a salt against the fluorescent whitening agent added to the developer. As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, potassium bromide and sodium bromide are preferable.

When it is eluted from the light-sensitive material during development, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

 Details of the general formula (I) will be described below.

In the formula, R ₁ and R ₂ are independently -COOR ₅ , Represents -COR ₅ or -CN. R ₃ and R ₄ are hydrogen atoms,
Alkyl group or substituted alkyl group (eg, methyl group,
An ethyl group, a butyl group, a hydroxyethyl group),
R ₅ and R ₆ are each a hydrogen atom, an alkyl group or a substituted alkyl group (eg, methyl group, ethyl group, butyl group, hydroxyethyl group, phenethyl group, etc.), aryl group or substituted aryl group (eg, phenyl group, hydroxyphenyl group). Etc.).

Q ₁ and Q ₂ each represent an aryl group (eg, phenyl group, naphthyl group, etc.). X ₁ and X ₂ represent a bond or a divalent linking group, and Y ₁ and R ₂ represent a sulfo group and a carboxyl group, respectively. L ₁ , L ₂ and L ₃ each represent a methine group. m ₁ , m ₂ is 0, 1 or 2, n is 0, 1 or 2, p ₁ , p ₂ are 0, ₁ , 2, 3 or 4, s ₁ ,
s ₂ represents 1 or 2, and t ₁ and t ₂ represent 0 or 1, respectively. However, m ₁ , p ₁ and t ₁ and m ₂ , p ₂ and t ₂ are never 0 at the same time.

Specific examples are shown below, but the present invention is not limited to these.

The amount of the compound of the general formula (I) used is preferably 0.0001 g to 1 g, more preferably 0.000 g / m ^{2 of the} color photographic light-sensitive material.
It is 5g to 0.1g.

The dye of formula (I) is usually used as an anti-irradiation dye. It is usually used in a silver halide emulsion layer, but it is particularly preferably added to a green-sensitive emulsion layer or a red-sensitive emulsion layer.

In the present invention, from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog, it is preferable that the color developer contains substantially no sulfite ion, but in order to suppress deterioration of the developer, Do not use the developer for a long time, use a floating pig to suppress the influence of air oxidation, use physical means such as reducing the opening of the developing tank, suppress the temperature of the developer, or use an organic preservative. And other chemical means can be used. Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent due to air or the like, among them, hydroxylamine derivatives (excluding hydroxylamine; hereinafter the same), hydroxamic acids, hydrazines, hydrazides, phenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-188619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
6559, 61-170756, 61-188742, 61-1887
No. 41, U.S. Pat.Nos. 3,615,503 and 2,494,903,
52-143020 and JP-B-48-30496.

Regarding the preferable organic preservatives, general formulas and specific compounds thereof are listed below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.0005.
Mol / l to 0.5 mol / l, preferably 0.03 mol / l to 0.1 mol
It is desirable to add so that the concentration becomes / l.

Particularly, addition of hydroxylamine derivative and / or hydrazine derivative is preferable.

The hydroxylamine derivative is preferably one represented by the following general formula (II).

General formula (II) In the formula, R ²¹ and R ²² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R ²¹ and R ²² do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with a nitrogen atom. The heterocyclic ring structure is a 5- or 6-membered ring and is composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

It is preferable that R ²¹ and R ²² are an alkyl group or an alkenyl group, and the carbon atom number is preferably 1 to 10, and particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by linking R ^{21 to} R ²² include a piperidine group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, a benztriazole group, and the like.

Preferred substituents for R ²¹ and R ²² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (III) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. The heterocyclic group is a 5- to 6-membered ring,
It is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. X ³¹ is -CO-, -SO ₂
-Or Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In the general formula (III), R ³¹ , R ³² and R ³³ represent a hydrogen atom or C ₁ to
Preferably represents an alkyl group of C _10, in particular R ^31, R ³²
Is most preferably a hydrogen atom.

In formula (III), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Preferred substituents of the alkyl group here are carboxysyl group, sulfo group, nitro group, amino group, sulfono group and the like. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

(Compound example) _{III-2 NH 2 NHCH 2 4} SO 3 H III-3 NH 2 NHCH 2 2 OH _{III-6 NH 2 NHCOCH 3 III} -7 NH 2 NHCOOC 2 H 5 III−10 NH ₂ NHCONH ₂ III-12 NH ₂ NHSO ₃ H III-14 NH ₂ NHCOCONHNH ₂ III-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H III-18 NH ₂ NHCH ₂ CH ₂ COOH Use of the compound represented by the general formula (II) or (III) and the amine represented by the following general formula (IV) or (V) in combination improves the stability of the color developer. Is more preferable from the viewpoint of improving the stability during the coupling treatment.

General formula (IV) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R
⁷³ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

(Example of compound) IV-1 NCH ₂ CH ₂ OH) ₃ IV-2 H ₂ NCH ₂ CH ₂ OH IV-3 HNCH ₂ CH ₂ OH) ₂ IV-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ IV-11 HNCH ₂ COOH) ₂ IV−13 H ₂ HCH ₂ CH ₂ SO ₂ NH ₂ IV-15 H ₂ N-CCH ₂ OH) ₂ General formula (V) In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other.

Of the general formula (V), particularly preferred are those of the general formula (V
-A) and (Vb).

In the formula, X ¹ represents N or CH. R ¹ and R ² are defined as in the general formula (V), R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (Va), X ¹ is preferably N. The carbon number of R ¹ , R ² and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (V).

In the general formula (Vb), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (Va) and (Vb), the compound represented by the general formula (Va) is particularly preferable.

The organic preservative can be obtained as a commercial product, but can also be synthesized by the method described in Japanese Patent Application Nos. 62-124038 and 62-24374.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples thereof are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N- (Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per developing solution.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11,0. The color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, NN-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3-diamino- 2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-
Sulfosalicylic acid, 4-sulfosalicylic acid, and these chelating agents may be used in combination of two or more, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, etc., p shown in JP-A Nos. 52-49829 and 50-15554. -Phenylenediamine compounds, JP-A-50-13
7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in U.S. Pat.Nos. 2,610,122 and 4,119,462, and U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Japanese Patent Sho 4
1-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in JP-B-3.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxides represented by 532, 501, etc.,
In addition, 1-phenyl, 3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

The color developer preferably contains substantially no benzyl alcohol. Substantially per color developer
The amount is 2.0 ml or less, more preferably, it is not contained at all.
When it is not substantially contained, variation in photographic characteristics during continuous processing, especially increase in stain is small, and more preferable results are obtained.

In the present invention, any antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole and 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 10 g / l, preferably 0.1 to 6 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The effect of the present invention is remarkable when the processing time of the color developing solution of the present invention is 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. When the treatment temperature is 33 to 45 ° C., preferably 36 to 40 ° C., the effect of preventing stain is particularly remarkable.

The replenishing amount of the color developing solution during continuous processing is preferably ^{20 to} 220 ml, and particularly 40 to 140 ml per 1 m ² of the light-sensitive material from the viewpoint that the effects of the present invention can be effectively exhibited.

In the present invention, desilvering processing is performed after color development.
The desilvering step generally comprises a whitening step and a fixing step, but it is particularly preferable that the desilvering steps are performed simultaneously.

The whitening solution or bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), or chloride (eg, potassium chloride,
Rehalogenating agents such as sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. These are used alone or in admixture of two or more. can do. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5.
The range is up to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is
3-8 are preferable and 4-7 are especially preferable. pH
If it is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing solution in the present invention include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) as preservatives, bisulfites (for example, ammonium bisulfate sulfate, sodium bisulfite, potassium bisulfite, Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound is contained. These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / l in terms of sulfite ion, more preferably 0.04 to 0.40 mol / l. Particularly, addition of ammonium sulfite is preferable.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, carbonyl bisulfite adduct, sulfinic acid, carbonyl compound, sulfinic acid, etc. may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

The bleach-fixing solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. The replenishment rate is 30 per 1 m ² of light-sensitive material.
It is ml-250 ml, preferably 40 ml-150 ml. Generally, as the replenishment amount is decreased, stain is increased and desilvering failure is likely to occur, but according to the present invention, the replenishment amount of the bleach-fixing solution can be reduced without causing such a problem. You can

The silver halide color photographic light-sensitive material of the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, and then washing with water and / or a stabilizing step.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the application, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers) Volume 64, p.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the air-killing agents described in "Sterilization, Sterilization, and Antifungal Technologies of Microorganisms" edited by the Society of Hygiene Technology, "Encyclopedia of Antibacterial and Antifungal Agents", edited by Japan Society for Antibacterial and Antifungal Agents.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C for 20 seconds to 2 minutes, preferably 25 to 40 ° C for 30 seconds to 1 minute 30 seconds. Is selected.

Even in such a short time water washing, according to the present invention,
Good photographic characteristics can be obtained without increasing stain.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
No. 59, No. 184343, No. 60-220345, No. 60-238832
No. 60, No. 60-239784, No. 60-239749, No. 61-4054,
All known methods described in JP-A-61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-
A stabilizing bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and for example, it is used as a final bath of a color light-sensitive material for photographing. A stabilizing bath containing formalin and a surfactant can be mentioned.

The processing step time of the present invention is defined as the time from the contact of the light-sensitive material with the color developing solution to the final bath (generally washing with water or stabilizing bath). The processing step time is 3 minutes. The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 3 minutes or less.

Next, the silver halide color photographic light-sensitive material used in the present invention will be described in detail.

The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. There are many useful points in terms of photosensitivity, such as increasing the light absorption amount, enhancing the adsorption of the spectral sensitizing dye, or weakening the desensitization by the spectral sensitizing dye.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have a phase different from the inside and the surface layer, may have a multiphase structure having a bonding structure, or may have a uniform whole grain. It may consist of phases. Moreover, they may be mixed.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those having a regular crystal form such as tetradecahedron, spherical,
It may be a material having an irregular crystal such as a plate, a material having a crystal defect such as a twin plane, or a compound thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978).
Dec.), pp. 22-23, "I. Emulsion prepara
and types can be prepared using the methods described in "

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,430,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

The sensitizing dye used in the present invention is a continuous processing of a color photographic light-sensitive material consisting of high silver chloride developed with a color developer containing a constant concentration of chlorine ion and bromine ion,
Alternatively, the compounds represented by the following general formulas (a) and (b) are preferable in terms of further improving the degree of stain generated after processing and further improving the stability of photographic characteristics.

General formula (a) In the formula, L represents a methyl group or a substituted methine group, and R ¹¹
And R ¹² each represents an alkyl group or a substituted alkyl group, Z ₁ and Z ₂ each represent an atomic group forming a nitrogen-containing 5- to 6-membered heterocyclic nucleus, and X represents an anion. n represents a numerical value of 1, 3, or 5, n ₁ and n ₂ are 0 or 1, respectively, and when n = 5, both n ₁ and n ₂ are 0.
And when n = 3, either N ₁ or n ₂ is 0. m represents 0 or 1, but is 0 when forming an intramolecular salt. When n is 5, L's may be linked to each other to form a substituted or unsubstituted 5-membered or 6-membered ring.

The cyanine dye represented by formula (VIa) will be described in detail below.

Examples of the substituent of the substituted methine group represented by L include a lower alkyl group (eg, methyl group, ethyl group, etc.) and an aralkyl group (eg, benzyl group, phenethyl group, etc.).

The alkyl residue represented by R ¹¹ and R ¹² may be linear or branched, or cyclic. The number of carbon atoms is not limited, but is preferably 1 to 8, and particularly 1 to 4
Is particularly preferable. Further, examples of the substituent of the substituted alkyl group include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, an alkoxy group, an acyloxy group, and an aryl group (for example, a phenyl group, a substituted phenyl group, etc.). These groups may be bonded alone or in combination of two or more to the alkyl group. Further, the sulfonic acid group and the carboxylic acid group may form a salt with an alkali metal ion or a quaternary ion of an organic amine. Here, the combination of two or more includes the case where these groups are independently bonded to an alkyl group and the case where these groups are linked and bonded to an alkyl group. Examples of the latter include a sulfoalkoxyalkyl group, a sulfoalkoxyalkoxyalkyl group, a carboxyalkoxyalkyl group and a sulfophenylalkyl group.

Specific examples of R ¹¹ and R ¹² are methyl group, ethyl group, n-propyl group, n-butyl group, vinylmethyl group,
2-hydroxyethyl group, 4-hydroxybutyl group, 2
-Acetoxyethyl group, 3-acetoxypropyl group, 2
-Methoxyethyl group, 4-methoxybutyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2- (2
-Carboxyethoxy) ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
Sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2- (3-sulfopropoxy) ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2-
(3-sulfopropoxy) propyl group, 2- [2- (3
-Sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3- (3'-sulfopropoxy) propyl group and the like.

Specific examples of the nitrogen-containing heterocyclic nucleus formed by Z ₁ or Z ₂ include oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, imidazoline nucleus, and these. Examples thereof include those in which a benzene ring, a naphthalene ring, or other saturated or unsaturated carbocycles are condensed, and these nitrogen-containing heterocycles further have a substituent (for example, an alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, a cyano group). Group, carboxylic acid group, carbamoyl group, alkoxy group, aryl group, acyl group, hydroxyl group, halogen atom, etc.) may be bonded.

Examples of the anion represented by ^{X, Cl -, Br -,} I -, SO
_{^{4 -, NO 3 -, ClO}} 4 - and the like can be given.

Among the cyanine dyes represented by the general formula (VIa), those preferable for the yellow layer and the cyano layer are shown below as specific examples.

Next, preferable sensitizing dyes are shown in the green-sensitive emulsion layer. General formula
(VIb) Where Z₁And Z₂Is benzene fused to each heterocycle
List the atoms required to form a ring or naphthalene ring.
You The heterocyclic nucleus formed may be substituted with a substituent
Yes. R₁And R₂Is an alkyl group, an alkenyl group or
Represents an aryl group, R₃Is a hydrogen atom or an atom having 1 to 3 carbon atoms.
Represents a rukyl group. X₁ Represents an anion, p is 0 or 1
Represents Y₁And Y₂Is an oxygen atom, a sulfur atom, a selenium atom,
Represents a nitrogen atom and a terium atom.

Preferred substituents among the substituents for the heterocyclic nucleus formed are a halogen atom, an aryl group, an alkenyl group,
An alkyl group and an alkoxy group. More preferable substituents are a halogen atom, a phenyl group and a methoxy group,
The most preferred substituent is a phenyl group.

Preferably, Z ₁ and Z ₂ are both a benzene ring or a thiazole ring fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or The 5-position is a phenyl group, and the 5-position of another benzene ring is substituted with a halogen atom. R ₁ and R ₂ are each a group selected from an alkyl group, an alkenyl group and an aryl group, preferably an alkyl group substituted with a carboxyl group or a sulfo group, and most preferably a sulfo group having 1 to 4 carbon atoms. It is an alkyl group, and most preferably a sulfoethyl group. R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

The sensitizing dye represented by the general formula (VIb) used in the present invention can be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, the respective sensitizing dyes may be dissolved in the same or different solvents, and these solutions may be mixed or separately added to the emulsion prior to addition to the emulsion. When they are added separately, their order and time interval can be arbitrarily determined according to the purpose.

Specific compounds of the sensitizing dye represented by the general formula [VIb] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

Usually, in order to spectrally sensitize a silver halide emulsion, a method is used in which after a grain is completely formed, a spectral sensitizing dye is adsorbed on the surface of the grain. On the other hand, U.S. Pat.No. 2,735,766 discloses a method of adding a merocyanine dye during the precipitation formation of silver halide grains, and it is remembered that the dye that does not adsorb can be reduced thereby. . Japanese Patent Application Laid-Open No. 55-26589 discloses a method in which a silver sensitizing dye is added during the addition of an aqueous solution of a silver salt or an aqueous solution of a halogen salt to form silver halide crystal grains and is adsorbed. As described above, the spectral sensitizing dye may be added during the formation of the silver halide crystal grains, after the formation thereof, or before the formation thereof. Specifically, before the formation is started, the spectral sensitizing dye may be introduced into the reaction vessel in advance before the reaction for forming the silver halide crystal is started. The term "after the particle formation is completed" means that the particles are adsorbed after the substantial particle formation process is completed. The silver halide emulsion of the present invention is chemically sensitized after the completion of grain formation. However, addition of the spectral sensitizing dye after the completion of grain formation can be performed during the chemical sensitization even before the start of such chemical sensitization. Or after the chemical sensitization, or when the emulsion is used for coating. In the present invention, it is preferable that the above-mentioned addition of the spectral sensitizing dye is added and adsorbed in at least one step of any step after the step in which the formation of silver halide grains is substantially completed. It may be added over two or more steps or dividedly. Moreover, in one process, it may add intensively in a short time, or may add continuously over time. Some of these addition methods may be combined.

The spectral sensitizing dye to be added may be added as it is as a crystal or powder, but it is preferable to add it by dissolving or dispersing it by any method. 1 carbon to dissolve
3 to water, a water-soluble solvent such as acetone, pyridine, methyl cellosolve, or a mixed solvent thereof. Further, a surfactant may be used to disperse the micelles or to disperse the other.

The addition amount of the spectral sensitizing dye depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but it is usually from 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide. Mol, more preferably 1 × 10 ⁻⁵ to 5 × 10 ⁻³ mol.

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are Research Disclosure Vol. 176, No. 17643 (December 1979) and No. 187.
Volume, No. 18716 (November, 1979), the relevant parts are summarized in the table below.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760 and the like are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
619, 4,351,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, European Patent 161,626A and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,358 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in U.S. Pat.
Examples thereof include DIR redox compound releasing couplers described in JP-A-185950 and the like, and couplers which release a dye that recovers color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the present invention, it is preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

Preferred compound (F) has a second-order reaction rate constant k2 with p-anisidine (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec. A compound that reacts. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the residual aromatic amine-based developing agent is slow, and as a result, the side effect of the residual aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R _1- (A) _n -X General formula (FII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which reacts with an aromatic amine type developing agent to form a chemical bond, and X represents a group which reacts with an aromatic amine type developing agent and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y accelerates the addition of the aromatic amine developing agent to the compound of the general formula (FII). Represents the group Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine-based developing agent, representative ones are substitution reaction and addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545, JP-A-62-283338, JP-A-62-158342, and JP-A-63-18439. What is described in the specification of this is preferable.

On the other hand, a more preferred compound (G) that chemically bonds with the oxidation product of the aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and colorless compound is represented by the following general formula (GI ).

General formula (GI) RZ In formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilicity ⁿ CH ₃ I (RG Pearson, et
al., J.Am.Chem.Soc., 90, 319 (1968) whether 5 or more groups,
Alternatively, groups derived therefrom are preferred.

Specific examples of the compound represented by the general formula (GI) are described in European Patent Publication No. 255722, JP-A-62-143048, and JP-A-62-143048.
No. 229145, Japanese Patent Application No. 63-18439, No. 63-136724, No. 62
Preferred are those described in JP-A-214681 and JP-A-62-158342.

Details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD, No, 17643, page 28, and No. 18716, page 647, from the right column
See page 648, left column.

The light-sensitive material to which the present invention is applied is, for example, a color photographic light-sensitive material such as a color negative film, a color reversal film (inner type and outer type), a color paper, a color positive film, a color reversal paper, a color diffusion transfer process, and a direct positive color light-sensitive material. Any of the above may be used, but it is particularly preferably applied to color paper, color auto positive paper, and color reversal paper.

(Examples) Examples of the present invention will be specifically shown below.
It is not limited to these.

Example 1 A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic with an average grain size of 0.85μ, a grain size distribution variation coefficient of 0.07, and contains 1.0 mol% of silver bromide localized on a part of the grain surface) of the two blues shown below. A sensitizing dye was added at 2.0 × 10 ⁻⁴ mol per mol of silver and then sulfur-sensitized. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation. (4 mg / m ² each) (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluing dye (ultraviolet)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.85 Yellow coupler ( ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Color image stabilizer (Cpd-7) 0.03 Solvent (solv-3) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (solv-4) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic with grain size 0.40μ, coefficient of variation 0.09, 1 mol% of silver bromide is a part of grain surface) 0.25 Gelatin 1.24 Magenta coupler (ExM) 0.29 Color image stabilizer (Cpd-3) 0.09 Color image stabilizer (Cpd-4) 0.06 Solvent (solv-2) 0.32 Solvent (solv-7) 0.16 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent solv-5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic with a grain size of 0.36μ and a coefficient of variation of 0.11 and containing 1.6 mol% of silver bromide localized on a part of the grain surface) 0.21 Gelatin 1.34 Cyan coupler (ExC) 0.34 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.34 Color image stabilizer (Cpd-9) 0.04 Solvent (Solv-6) 0.37 Sixth layer (UV ray) Absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The sample obtained as described above was designated as IA. Next, instead of the anti-irradiation dyes (I-4, I-36), the following dyes were changed to prepare samples IB to IE.

The following experiments were conducted in order to examine the photographic characteristics of the coated samples I-A to I-E.

First, the coated sample was subjected to sensitometric gradation exposure using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1 /
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 10 seconds.

The coating sample is subjected to the following treatment steps and treatment compositions,
Processed using an automatic processor. However, the composition of the color developing solution was changed as shown in Table 1. Processing steps Temperature Time Color developing 38 ° C. 45 seconds blix 30 to 36 ° C. 30 sec Rinse 30 to 37 ° C. 20 sec Rinse 30 to 37 ° C. 20 sec Rinse 30 to 37 ° C. 20 sec Drying 70 to 80 ° C. 60 seconds each processing solution The composition is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0 g Preservative III-19 5.0 g Sodium chloride See Table 1 Potassium bromide See Table 1 Potassium carbonate 25 g N-Ethyl-N -(Β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulphate 5.0g Triethanolamine 10.0g Fluorescent brightener (Sumitomo Chemical Co., Ltd., WHITEX4) 2.0g Water added 1000ml pH (25 ℃ ) 10.05 Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution Ion exchange water (Karishiumu, magnesium each 3ppm or less) processing said sample, minimum density and maximum density of the cyan _{(R) (D R min,} D R max) at the Macbeth densitometer It was boss.
Further, the maximum residual silver amount was measured by fluorescent X-ray.

By treating Samples IA, B and C of the present invention with Treatments 3, 4, 5 and 6 of the present invention, good stains of cyan, high maximum density and low residual silver amount were obtained. It has been found that photographic properties are obtained.

In samples I-D and I-E having anti-irradiation dyes other than the present invention, the above effect could not be obtained even in the treatment of the present invention.

(Example 2) The preservative in the color developer in Treatment 4 of Sample Example 1
Instead of III-19, equimolar preservatives II-1, II-2, III
When Sample IA was processed by changing to -11 and III-21 respectively, similarly excellent photographic characteristics could be obtained.

Example 3 Instead of the anti-irradiation dye of Sample 1-A of Example 1, I-1, I-3, I-5, I-9, I-12,
A sample containing 8 mg / m ² of each of I-18, I-25, I-30, and I-37 was prepared and treated in the same manner as in Example 1,
Excellent photographic properties were obtained in Processes 3-6 of the present invention.

(Example 4) Example 4-Same as Sample 1-A, but Sample 4-using a silver chlorobromide emulsion with the silver bromide content changed as follows:
A, B, C and D were prepared and treated in Examples 1, treatments 2, 4 and 7 and the results are shown in Table 2.

Treatment of Samples 1-A, 4-A, 4-B, and 4-C of the present invention with Treatment 4 of the present invention yielded excellent characteristics with low stain, high maximum density, and low residual silver content. In particular, the effect is remarkable in Samples 1-A and 4-A using a silver chlorobromide emulsion having chloride ions of 95 mol% or more.

Example-5 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the following layer constitution was produced. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, in a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution variation coefficient 0.08, 0.2 mol% of silver bromide contained on the grain surface), the following blue-sensitizing sensitizing dyes were each added in an amount of 2.0 × per mol of silver. After addition of 10 ⁻⁴ mol, a sulfur-sensitized product was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1 as a gelatin hardening agent for each layer
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv -1) 0.16 Solvent (Solv-4) 0.08 Third Layer (Green Sensitive Layer) Silver chlorobromide emulsion (1: 3 mixture (Ag mole) ratio of cubic average grain size 0.55μ and 0.39μ). Coefficients of variation of particle size distribution 0.10, 0.08, and AgBr 0.8 mol% were contained locally on the particle surface. 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.54 Fourth layer ( UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic average particle size 0.58) 1: 4 mixture of μ and 0.45μ (Ag molar ratio), variation coefficient of particle size distribution 0.09, 0.11, and AgBr 0.6mol% were locally contained in a part of the grain surface 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer (UV absorption) Layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic-modified copolymer of polyvinyl alcohol (modification degree 17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The sample obtained as described above was designated as Sample 5-A.
Next, a sample using the same anti-irradiation dye as in Example 1 Sample 1-D was designated as Sample 5-B.

After the imagewise exposure of each of Samples 5-A and 5-B, continuous processing was carried out in the following processing steps until the amount of the color developing tank was replenished by 3 times.

The composition of each treatment liquid is as follows.

Rinsing solution (same as tank solution and replenisher) Ion-exchanged water (3p each for calcium and magnesium)
pm or less) For color developing solution, bleach-fixing solution and washing solution,
Distilled water was added in an evaporation amount, and continuous processing was performed while correcting the evaporation concentration.

After continuous processing, the chlorine ion and bromine ion concentrations in each color developing solution were analyzed, and the results were equally as follows.

Cl ^-1 Br ^- 5-A similar to the continuous process after ^{5.5 × 10 -2 M 2.0 × 10} -4 M continuous treatment after ^{5.5 × 10 -2 M 2.0 × 10} -4 M following Examples 1 5-B of Then, the samples 5-A and 5-B were exposed for sensitometry, treated with the respective treatment solutions, and D _R min, D _R max and the residual silver amount were determined as follows.

According to the present invention, the stain is low, the maximum concentration is high,
Excellent photographic characteristics with a small amount of residual silver were obtained.

(Example 6) Next, the irradiation preventing dye and the sensitizing dye of Example 5, Sample 5-A were changed as shown in Table 3 to prepare Sample 6-.
A, B, C, D, E and F were prepared.

After the sensitometric exposure of each of the above samples, the sample was treated with the treated solution of Example 5, Sample 5-A to obtain D _B min and D _R mi.
n, were measured D _B max and residual silver. The results are shown in Table 4.

According to the present invention, not only an excellent white background having a low yellow or cyan stain can be obtained, but also the maximum density is high and the residual silver amount is small. The effect is remarkable in Samples 6-E and 6-F using the particularly preferred sensitizing dye.

Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, wherein a high silver chloride halogen content of 80 mol% or more of silver chloride is used. A silver halide color light-sensitive material having at least one layer of a silver halide emulsion and at least one layer of a compound represented by the following general formula (I) is used. Chloride ions of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 Mol / l contained,
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing bromine ions in an amount of 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l. General formula (I)